Production of organometallic compounds



2,909,565 Patented Oct. 20, 1959 PRODUCTION OF ORGANOMETALLIC COMPOUNDSDavid 0. De Pree, Baton Rouge, La., assignor to Ethyl Corporation, NewYork, N. Y., a corporation of Delaware No Drawing. Application February6, 1958 Serial No. 713,569

5 Claims. (Cl. 260-541) This invention relates to a process for thepreparation of organometallic compounds and in particular is conin whichthe .a-carbon atom of a metal salt of an organic acid is substitutedwith a metal.

The prior art discloses processes for the preparation of u-metallicsubstituted organic salts such as a-sodiosodium ethyl acetate. Ingeneral, these processes involve the consumption of two equivalents ofmetal for each equivalent ofthe a-metallo-metallic salt of an organicacid produced. For example, 'a-SOdiO-sOdiIlm caproate is described asbeing formed when reacting sodium caproate concurrently with sodium andbenzene and passing amyl chloride through the reaction mixture. Thus,the sodium reacts with the amyl chloride in situ to produce amyl sodiumand sodium chloride, thus consuming two equivalents of the metal. Theamyl sodium then reacts with the sodium caproate to producem-sodio-sodium caproate. In addition, the processes taught in the artresult in the formation of other organometallic compounds which hinderthe separation of the a-metallo-metallic compounds and because of theseimpurities limits their usage since these foreign compounds undergocompet ing reactions. Further, the process encompasses a complexity ofundesirable side reactions difficult to control. An improvement to theprocesses described above is the reaction between metallic amides andmetal salts of equimolar quantities of the alkali metal and the alkalimetal salt of the aforesaid carboxylic acid. The reactants should alsobe preponderantly anhydrous and preferably of a small particle size.Additionally the starting materials should be essentially free oforganometallic compounds or compounds that would form organometalliccompounds other than the products desired. In one embodiment thecatalyst and reactants are prepared in'the reaction vessel and heated inan inert atmosphere to initiate the'reaction. The pressures employed areessentially atmospheric and volatile by-products are continuouslyremoved. A preferred example of the aforementioned especially preferredembodiment comprises reacting sodium acetate with sodium in the presenceof catalytic amounts of sodamide employing atmospheric I pressure andtemperatures below 280 C. cerned with the preparation of organometalliccompounds pounds is quite diflicult.

Aparticular advantage of the process of this invention is that theproducts obtained are substantially in their pure form in high yield.The purity of the product obtained is important since its separationfrom other com- If other organometallic compounds were present, as forexample, amyl sodium, these materials would react competitively with themetallomoles of sodium per mole of product or the employment organicacids whereby utilization of equal equivalents T in a metal salt of anorganic acid and a metal are reacted.

It is an object of this invention to provide a new process. A particularobject is to provide a process for the preparation of a-metallicsubstituted metal salts of organic acids in high yield and purity.

of a sodamide rather than the economical sodium metal.

To more fully demonstrate the process of this invention, the followingworking examples in which all parts and percentages are by Weight arepresented.

Example I Into a reaction vessel provided with means for charging,heating, stirring, and additionally provided with fittings for inlet andoutlet of nitrogen was added 113 parts of anhydrous sodium acetate. Anitrogen flush was started and the system was heated at 261 to 274 C.for one hour. Thereafter 30 parts of sodium was added in small piecesfollowed by the addition of a catalytic amount of sodium amide (1.4parts). The nitrogen was discontinned and the reaction conditionsmaintained for 3% The above and other objects ofthis invention areaccomplished by reacting an alkali or alkaline earth metal salt of anorganic acid containing at least one a-hydrogen atom with a metal in thepresence of a catalyst selected from the group consisting of metalamides and metal hydrides. Each of the aforesaid metals is selected fromthe group consisting of alkali and alkaline earth metals. In general, itis preferred to employ alkali metals and the salt of a carboxylic acidhaving at least one a-hydrogen atom.

In an especially preferred embodiment the metal salts perature. It isalso preferred to employ substantially hours.

The system was then shut down. A nitrogen flush was started. Stirringwas stopped at 70 C. When the reactor cooled to room temperature theproduct was withdrawn. To a sample of the reaction product weighingapproximately 1 gram was added under nitrogen atmosphere 3 millilitersof deuterium oxide in a slow manner. Excess deuterium oxide was removedinto vacuo in a drying pistol. When all the liquids had been removed,the pistol was heated under vacuum at 140 for 16 hours to decompose anyresidual hydrate. The anhydrous product was heated at C. with an excessof dimethyl sulfate and the methyl acetates formed were condensed andexamined with a mass spectrometer. From the ratio of the peaks themoleratio of a-sodio-sodium acetate to sodium acetate in the sample wasdetermined to be 8.55:1 corresponding to approximately 91 percent yieldof oc-SOdiO-SOdilltn acetate based on total conversion of sodiumacetate.

No reaction was initiated when the above reaction was repeated utilizingessentially the same reaction conditions with the exception that nosodamide catalyst was employed.

The following working examples illustrate the undesirability ofutilizing low temperatures in the process of this invention'that is,temperatures markedly below the range extending from the decompositiontemperature of the product formed to 20 degrees less than saiddecomposition temperature.

Example II Three parts of sodium chloride were placed in a reactionvessel provided with means for heating, stirring, and gas inlets andoutlets. Ten parts of sodium were added to the vessel. The vessel washeated to 200 C. whereupon 35.28 parts of sodium acetate were added tothe reaction. Nitrogen flushing was initiated and temperature in thesystem dropped to 175 C. whereupon 0.64 part sodamide was added. Thetemperature was then raised to 228 C. and reaction conditions maintainedfor 4- hours. The system was cooled and mass spectrometer analysisindicated a low yield of the desired product a-sodio-sodium acetate.

The following examples illustrate that salts of organic acids other thansodium acetate can be utilized.

Example III a-Sodio-sodium phenyl acetate is prepared by the reaction ofsodium phenyl acetate with sodium in the pres ence of catalytic amountsof sodamide utilizing procedures essentially the same as described inExample 1.

Example IV a-Sodio-sodium vinyl acetate is prepared by reacting sodiumvinyl acetate with sodium in the presence of catalytic amounts ofsodamide essentially as described in Example I.

Example V 180 parts of 2-cyclopentyl sodium acetate and 39.1 parts ofpotassium are reacted in the presence of 1.91 parts of potassium amideessentially the same as described in Ex ample I. The producta-potassio-2-cyclopentyl sodium acetate is thereby prepared.

Example VI The procedure of Example I is followed with the exceptionthat 156 parts of Z-benzyl lithium acetate and 14.6 parts of magnesiummetal utilizing 2.12 parts of magnesium hydride to produce the producta-magnesium-Z- benzyl lithium acetate.

Other starting materials, other than those taught in the above examples,can be employed with equal results. Thus, the organic portion of themetal salt of an organic acid containing at least one a-hydrogen atomdenotes a univalent, aliphatic or alicyclic or aromatic radical whichcan be further substituted. By the term organic portion is meant thatpart of the acid salt other than the carboxylic functional group,

OG By the term univalent aliphatic is intended a univalent radicalderived from an, open chain saturated or unsaturated carbon compound.The term univalent alicyclic radical denotes a univalent radical derivedfrom the corresponding aliphatic compounds by ring formation. Thus, theorganic portion of the metal salt of an organic acid containing at,least one a-hydrogen atom can be radicals such as the alkyl radicals,methyl, ethyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-amyl, andvarious positional isomers such as, for example, Z-methylbutyl,1,2-dimethylpropyl, and l-ethylpropyl, and likewise, the correspondingstraight or branched chain isomers of hexyl, heptyl, octyl, and the likeup to and including about eicosyl. Moreover, suchrmonovalent aliphaticradicals can be alkenyl radicals suchas, for example, ethenyl, u-propenyl, isopropenyl, A -butenyl, A -butenyl, and the correspondingbranched chain isomers thereof, and other alkenyl radicals such ashexenyl, heptenyl, octenyl, up to and including eicosenyl, and theircorresponding branched chain isomers. Further, such monovalenthydrocarbon substituents can be aralkyl radicals such as, for example,benzyl, a-phenylethyl, ,B-

107:1 deuterated to non-deuterated material.

4 phenylpropyl, 'y-phenylpropyl, fl-phenylisopropyl, u-phenylbutyl,-phenylbutyl, and the like, and a'-naphthylmethyl, a-(aJ-naphthyD-ethyl,u-(p-naphthyl)-ethyl, and the like, and their corresponding positionalisomers. Moreover, the univalent aliphatic radical or radicals can bearalkenyl radicals such as, for example, u-phenyl ethenyl, a-phenyl-A-propenyl, ,e-phenyl-A -propenyl, a-phenyl-A propenyl,et-phenylisopropenyl, ,B-phenylisopropenyl, and similarly, the phenylderivatives of the isomers of butenyl, pentenyl, and the like. Othersuch. aryl alkenyls, include a-(a-naphthyl)-etheny1,,B-(aT-naphthyl)-ethenyl, a-(}3'- naphthyl)-A -propenyl,fi-(fl-naphthyl)-A -propenyl, a- (fi' naphthyl) A propenyl, a (a'naphthyl) isopropenyl, and the like.

When the monovalent hydrocarbon radical is a univalent alicyclic radicalor radicals, these can be selected from the group consisting ofcycloalkyl and cycloalkenyl radicals. Thus, for example, they can be thecycloalkyl radicals, cyclopropyl, cyclobutyl, cycloamyl, cyclohexyl, andthe like, and such cycloaliphatic radicals as a-cyclopropylethyl,B-cyclobutylpropyl, and the like. Similarly, the alicyclic radicals canbe cycloalkenyl radicals such as, for example, a-cyclohexyl ethenyl,a-cycloheptyl-A -propenyl, fl-cyclooctyl-A -propenyl, fl-cyclononylisopropenyl, and the like. When the monovalent hydrocarbon radical is aunivalent aromatic radical or radicals, these, can, be selected fromthe, group consisting of aryl and alkaryl radicals, for example, arylradicals such as phenyl, a-naph: thyl, fl-anthryl, and the like.Moreover, the univalent aromatic radical can be alkaryl radicals suchas, for example, o-tolyl, 2,3-xylyl, 2,4-xylyl, 2,6-xylyl, and the like,or o-ethylphenyl, p-ethylphenyl, Z-methyl-a-naphthyl, 4-methyl-ot-naphthyl, 7-methyl-a-naphthyl, and the like.

It is to be understood that the foregoing listing of radicals is merelyexemplary and other examples will be evident to those skilled in theart. Furthermore, these radicals can be substituted with othersubstituentsprovided they are inert to the reactants as, for example,ether linkages.

Exemplary of the alkali or alkaline earth metalsalts of organic acidswhich are employed as. reactants in this process are sodium acetate,lithium acetate, barium acetate, calcium acetate, sodium propionate,beryllium propionate, sodium isobutyrate, sodium valerate, lithiumdimethyl acetate, sodium. caproate, sodium heptylate, potassiumcaprylate, sodium pelargonate, calcium vinyl acetate, magnesium phenylacetate, sodium fi-naphthyl acetate, lithium benzyl acetate, sodiumphenyl ethenyl acetate, sodium cyclohexyl acetate, potassiumcyclopentadienyl acetate, sodium fl-methoxy methyl butyrate, and :thelike.

Another. embodiment of the instant process is the usage of a metalhydride catalyst. The following examples more fully illustrate thisembodiment. Example VII further illustrates that the catalyst of thisinvention can be prepared in situ in some instances.

Example VII In a reaction vessel provided with means for heating,

parts mineral oil, 11.5 parts sodium and 41 parts anhydrous, sodiumacetate. The temperature was gradually raised to C. in high speedstirrer and nitrogen flush was initiated. The temperature was thenraised to 260 C. whereupon hydrogen was fed to the nitrogen swept flask.A vigorous reaction occurred with the product turning yellow. The flaskwas then cooled to room temperature and a sample of the product obtainedin the reaction was analyzed by essentially the same deuterationprocedure as described in Example I. The analysis showed a ratio of Thisdemonstrates that the reaction, formed u-sodio-sodium acetatecorresponding to a 58% conversionbased on total sodium acetate.

Example VIII m-Sodio-sodium caproate is prepared in essentially the samemanner as described in Example VII by the reaction between sodiumcaproate, sodium and catalytic amounts of sodium hydride.

Example IX a-Lithio-lithium-2-cyclohexyl acetate is prepared whenlithium is reacted with lithium-Z-cyclohexyl acetate in the presence ofcatalytic lithium hydride employing a process essentially the same asdescribed in Example VII.

Example X Catalytic amounts of barium hydride initiates the reactionbetween sodium propionate and barium to produce the desired productu-barium-sodium-propionate employing processes essentially the same asthose employed in Example VII.

The metals employed in this invention are alkali and alkaline earthmetals. More specifically, they are the group I-A and II-A metals of theperiodic chart of the elements (Handbook of Chemistry and Physics, 38thedition, Chemical Rubber Publishing Company, 1956). Examples of metalhydrides employed in the process are lithium hydride, sodium hydride,potassium hydride, rubidium hydride, beryllium hydride, magnesiumhydride, barium hydride, calcium hydride, and the like. Examples ofthose metal amides which can be employed are sodio amide, potassiumamide, magnesium amide, calcium amide, and the like. In addition,certain substi tuted metal amides comprising the metal salts of lowmolecular weight amines for distillation temperatures below 56 C. can beemployed. Illustrations are diethyl sodium amide, dimethyl lithiumamide, diethyl calcium amide, and other similar substituted amides.

The temperatures employed are those suflicient to initiate reaction.Furthermore, the reaction is conducted at a temperature below thedecomposition temperature of the product produced. It is preferred toconduct the process at a temperature ranging from the decompositiontemperature of the product produced to 20 less than said decompositiontemperature. For example, when reacting sodium and sodium acetate bestresults are obtained at temperatures below 280 C. but no lower than 260C. H

In general, atmospheric pressures are employed. It has been discoveredthat in some instance when the hy-. dride catalyst is employed, nominalpressure can be utilized. However, the amide catalyst requiresatmospheric conditions. Thus, the following working example illustratesthe utilization of pressure in the reaction between sodium acetate andsodium in the pres-.' ence of catalytic sodium hydride.

Example XI Into a pressure vessel provided with means for heat-- ing,continuous addition, and stirring are added 86 parts sodium acetate, 23parts of sodium, and 3 parts of so-., dium hydride. The system ispressured to a 100 p.s.i. with nitrogen and thereupon heated to 260 C.for a period of 2 hours. Upon completion of the reaction the productobtained analyzes for a-sodio-sodium acetate in substantial yields.

Subatmospheric temperatures can be employed and have the advantage ofenhancing removal of the volatile by-product thus obtaining a more rapidreaction and more complete shifting of the equilibrium.

Although equal molar quantities of the metal and the acid salts arepreferred, a 20% excess of either reactant can be employed. In mostcases, however, it is especially preferred to employ the metallic saltsof the organic acid in about a 5 to excess so that the metal employedcan be quantitatively consumed. In this manner the product obtained maycontain some metallic salts of organic acids, but this impurity has notbeen found detrimental in subsequent use in the a-metallo-metallic saltsof organic acids.

The amount of catalysts employed in the process can vary up to 5% of theweight of the metallic salts of an organic acid employed. As has beenexplained hereinbefore, the process of this invention is inoperablewithout the utilization of a catalyst and the limits as to the amount ofcatalysts employed are essentially dependent upon the amount necessaryto initiate a reaction.. In no case, however, is more than 5% of theweight of the organic acid salts employed. Utilization of catalyticquantities greater than this results in uneconomical operation, becauseof starting products which are lost in the system and which, as has beenexplained hereinbea fore, are diificultly separated from the end productand thus cannot be recycled'for elficiency of operation.

In some instances it is desirable to employ the metal reactant in itshigh surface form. By providing the metal in such a form better controlof reaction rates and temperatures are provided, yields can beincreased, induction periods'can be avoided, and such a form facilitatesadaptation to continuous operation. The preparation of the metalfor thisembodiment is accomplished by mixing the molten metal with a suitableinert solid material having a very large surface area, such as salt,carbon, or in some instances, the metal salt of the organic aci Althoughthe general reaction is generally run in the dry stateas describedhereinbefore for some purposes it is desirable to conduct the reactionunder an inert liquid blanket. One of the purposes of such an embodimentis to avoid oxygen contamination by impurities in the flushing gas.Another reason is that this inert blanket acts'as a solvent for hydrogenor ammonia gas when'used to produce the catalyst of this invention insitu. The inert liquid blanket employed is generally a high boilinghydrocarbon oil, such as mineral oil.

As was illustrated in Example VII hereinbefore, the catalyst can beproduced in the reaction in situ. This is accomplished by the reactionof a controlled amount of the ammonia or hydrogen gas with theappropriate metal. Such technique finds usage in such operationalprocedure as continuous methods for the most part. However, in generalit is preferred to pre-form the catalyst before its utilization in thereaction system.

The process of this invention is admirably suited to continuous methods.For example, the reactants separately or together in the properproportions, are continuously ground to desired particle size,transmitted to a heated movable reactor surface, the volatile by-product1s removed and recovered by recycling to the preparation of the metalamide or derivative thereof, and the product is continuously dischargedfrom the reactor. This and other modifications will be evident to thoseskilled in the art.

The particle size of the reactants is important. In general, it ispreferred to employ particle sizes below about 50 microns. The smallerthe particle size, the more intimate contact obtained between thereactants and shorter reaction periods are required. As'notedpreviously, the reactants are mixed in the reaction vessel and heated.Although not required, this is the preferableoperation since moreefiicient comminution of the reactants is obtained and economies ofoperation are realized. It should be understood that the reactants canalso be pre-ground or pre-mixed, and further can be fed to the reactorseparately in larger particle sizes and mixed and ground in situ. Thisis particularly true when the agitation provided in the reactor is ofthe type to provide grinding of the reaction mixture during the courseof the reaction. Employing the technique of the grinding along with theagitation enhances the contact between the reactants, thus providingmore complete rcaction; The suitable method of obtaining this objective'duce the metal salt in situ.

metallic compounds.

7 is to employ a ball mill as a reactor. Other apparatus can be employedwhich will be evident to those skilled in the art.

The reaction should be conducted in an. inert atmosphere such as argon,nitrogen, krypton, and the like. It is preferable that the inertatmosphere be pre-pun'fied so as to be substantially free of impuritiessuch as oxygen and moisture since these impurities may be taken up inthe product.

Although it is generally preferred to employ the metal salt of anorganic acid as described hereinabove, it is obvious that the free acidcan also be employed to pro- Such an embodiment although utilizing twoequivalents of metal for each equivalent of metallated product producednevertheless only employs one equivalent of metal in the metallation ofthe a-carbon position. This embodiment thus is consistent with thestoichiometry described hereinbefore.

Thus, by the process of the instant invention when sodium is reactedwith sodium propionate in the presence of dimethyl amino sodium,u-SOdlO-SOdiUIH propionate is prepared. Likewise, whenpotassium-4-methyl caproate is reacted with sodium in the presence ofsodium amide, a-sodio-potassium-4-methyl caproate is produced. Inaddition, when potassium is reacted with sodium vinyl acetate in thepresence of potassium diethyl amide, a-potassio-sodium vinyl acetate isprepared. Further more, when barium phenyl acetate is reacted Withsodium hydride, a-sodio-barium phenyl acetate is produced.a-Lithio-lithium isobutyrate is obtained when lithium isobutyrate isreacted with lithium in the presence of lithium hydride. The foregoingexamples are cited merely as illustrations and are not intended to belimitations. That is, other combinations of the radicals, materials, andmetals defined previously will be evident to those skilled in the art.

When reacting metalic salts of organic acids with metal hydridesaccording to this invention, the metallo substituted metallic salts oforganic acids, as described hereinbefore, are obtained essentially freeof other organo- That is, the products as obtained by our process arenot contaminated with more than about .5 by weight of otherorganometallic compounds. The process of this invention thus providesthese'prodnets in essentially pure form thereby permitting their utilityin a variety of chemical reactions without the hinderance of competingreactions and the formation of impurities in the final products. 7

Thus, for example, a-sodio-sodium-2-ethyl propionate andu-sodio-sodium-2-methyl butyrate when reacted with carbon dioxide resultin substituted malonic acids which are obtained in high purity andyields.

Furthermore, the compounds produced by the process of this invention canbe employed in the preparation of salts of organic acids as, forexample, when a-sodiosodium acetate is reacted with n-octyl bromide asillustrated in the following working example.

Example XII Into a reaction flask provided with means for heating andrefluxing were added 10.4 parts of oz-SOdlO-SOdillIIl acetate and 38.6parts of n-octyl bromide utilizing 50 parts of n-nonane as a diluent.The mixture was externally heated to reflux temperature (about 150 C.)and maintained at this temperature for 6 hours. The solid product formedwas then filtered from the reaction mixture. This product, consistingessentially of sodium decanoate, was dissolved in water and acidifiedwith hydrochloric acid. A yellow oil separated which was extracted threetimes with ether. Upon evaporation of the ether from the productdecanoic acid having a melting point of 27 C. was recovered in highyield.

Likewise, in Example XII equally good results are obtained with otherproducts produced by the process of this invention, such asa-potassio-potassium acetate, a-calcio-barium acetate, and the like.

Another way inwhich the compounds produced by the process of thisinvention find utility is in the manufacture of organic esters as, forexample, when an organic monohalide having at least one hydrogen atom onthe halogen substituted carbon atom is reacted with a metallosubstituted metallic salt of this invention. The following examples morefully illustrate this embodiment.

Example XIII Into a reaction vessel provided with means for heating andcontaining 104 parts of a-sodio-sodium acetate were added 420 parts ofbenzyl chloride. This mixture was then heated to 60 C. Vigorous reactiontook place which was completed within a few minutes concurrently with atemperature rise. The reaction mass became nearly solid. The productupon cooling to room temperature was filtered and the solids washed withhexane. The filtrate was vacuum distilled to remove benzyl chloride anda fraction boiling at 240 C. at 14 millimeters of mercury was collected.This fraction was redistilled at atmospheric pressure and a fractionboiling between 310-340 C. was analyzed and found to contain 81.6%carbon, 6.74% hydrogen, no nitrogen and less than 1% chlorine whichcompares with the benzyl ester of phenyl propionic acid which has 80.2%carbon and 6.7% hydrogen.

Example XIV By reacting 160 parts of a-sodio-sodium caproate with 253parts of benzyl chloride at C. as in the preceeding example, the benzylester of fi-butyl phenyl propionic acid is obtained.

Furthermore, the compounds produced by the process of this invention canbe utilized in the preparation of thio acids by the reaction of ametallo substituted metallic salt of an organic acid with sulfuremploying temperatures of at least about 100 C. A preferred example ofthis utility is the reaction of 60.3 parts of a-sodio-sodium acetatewith 32 parts of sulfur employing a toluene solvent and refluxtemperatures.

Having thus described the novel process of this invention, it is notintended that it be limited except as noted in the appended claims.

Iclaim:

1. A process for the preparation of u-metallo-metallic salts of organicacids which comprises reacting a metal salt of a carboxylic acidcontaining at least one u-hydrogen atom with a metal in the presence ofa catalyst selected from the group consisting of alkali metal amides,alkaline earth metal amides, alkali metal hydrides and alkaline earthmetal hydrides, said process being conducted at a temperature rangingfrom the decomposition temperature of the product produced to 20 lessthan said decomposition temperature.

2. The process of claim 1 wherein essentially atmospheric pressures areemployed when said catalyst comprises a metal amide, wherein the amountof said catalyst employed is less than 5% of the weight of saidcarboxylic acid salt.

3. A process for the preparation of a-sodio-sodium acetate whichcomprises reacting sodium acetate with sodium in the presence ofcatalytic amounts of sodamide employing atmospheric pressure and atemperature between 2-6'l and 274 C.

4. A process for'the preparation of a-SOdiO sodium acetate, whichcomprises reacting sodium acetate with sodium and a catalytic amount ofsodium hydride, the quantity of sodium hydride being less than 5% of theweight of the sodium acetate, and the reaction being conducted at atemperature of from 260 to 280 C. while mixing and stirring thereactants.

5, A process for the preparation of oc-SOdiO sodium I 9 i i i 10acetate, which comprises g iddium gi e wi References Cited in the fileof this patent sodium and a catalytic amount of sodamide, t e quantityof sodamide being less than 5% of the weight of the g 9 g (1938) sodiumacetate, and the reaction being" conducted under m ct v (1 atmosphericpressure at a temperature of from 260 to 5 Fmidlin ct 33 C'A"'8566 7(1939) 280 C. while mixing and stirring the reactants.

1. A PROCESS FOR THE PREPARATION OF A-METALLO-METALLIC SALTS OF ORGANICACIDS WHICH COMPRISES REACTING A METAL SALT OF A CARBOXYLIC ACIDCONTAINING AT LEAST ONE A-HYDROGEN ATOM WITH A METAL IN THE PRESENCE OFA CATALYST SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL AMIDES,ALKALINE EARTH METAL AMIDES, ALKALI METAL HYDRIDES AND ALKALINE EARTHMETAL HYDRIDES, SAID PROCESS BEING CONDUCTED AT A TEMPERATURE RANGINGFROM THE DECOMPOSITION TEMPERATURE OF THE PRODUCT PRODUCED TO 20* LESSTHAN SAID DECOMPOSITION TEMPERATURE.